Process for the preparation of color images using 2 - ureido phenolic couplers



' United States Patent Int. Cl. G03c 7/34 US. Cl. 96--55 4 ClaimsABSTRACT OF THE DISCLOSURE Photographic elements which contain aphenolic coupler having in the 2-position a radical of the formulawherein Y is NHCO, COHN, -NHSO or -SO NH and R is hydrogen, aryl, alkyl,or arylalkyl, are shown.

This invention relates to a process for the preparation of color images,particularly of blue-green photographic images, and to photographicmaterials useful in this process.

For the preparation of blue-green photographic images alpha-naphtholicand phenolic color formers have been known to be useful. Generally thesecolor formers have had substituents in the 2 or 3 position to thehydroxyl group, eg. carbonamido, acylamino, sulphonamido orsulphonacylamino substituents. The naphtholic color formers have beenpreferred, since the phenolic color formers tend to produce dyes whichare not satisfactorily stable to light and which tend to yellow uponaging due to residual color former.

In German Patent No. 1,163,144 (Nov. 11, 1962) the 2-ureido phenolsdisclosed as color formers for cyan dyes are not subject to the lightstability problems generally associated with phenolic cyan colorformers. However, the dyes produced by chromogenic development generallyhave an absorption maximum in the shorter wavelength region of thespectrum, e.g. in the range of 610 to 640 millimicrons, normally belowabout 645 millimicrons, and are accordingly not considered desirable forconventional subtractive color photography, in which cyan dyes havingabsorption maxima of at least 645 are preferred.

It has now been found that certain derivatives of 2- ureido phenols aresuitable for producing cyan dye images in a photographic film uponreaction with the oxidation products of a chromogen developer, such asp-diethylamino-aniline, and that the resulting cyan dyes are lightstable and have an absorption in the desired portion of the lightspectrum for a trichromic subtractive color film and process. TheseZ-ureido phenols have, in the 2-position, a substituent of the formulawherein Y is -NI-ICO, CONH, NHSO or --SO NH- and R is hydrogen, an arylgroup, an arylaliphatic group or an aliphatic group. In the accompanyingtable the color formers of German Patent No. 1,163,- 144 are compared tothe color formers of this invention, and the improved maximum absorptionof the latter is shown. The color couplers appearing in the table (Nos.I to XVIII) are prepared as follows:

Coupler I 10.9 g. of o-aminophenol was dissolved in dioxane. 21.75 g. ofp-isocyano benzene sulphonyl chloride was added to the hot solution,which was then refluxed for one hour and poured into a boiling solutionof 7.45 g. of aniline in dioxane and pyridine. After crystallizationfrom ethanol-water 36 g. of product, M.P. 203 -205 C., was separated.

Coupler II 2.43 g. of 2-[p-aminophenyl] ureidophenol was dispersed indioxane and pyridine, then 1.4 g. of benzoylchloride were added to themixture. The solution was refluxed and separated from any tar, and wasthereafter poured into diluted hydrochloric acid. 3.5 g. of product wasobtained, which was purified with an alcohol-water solution until aproduct melting at C. was obtained.

2-[p-aminophenyl] ureidophenol (M.P. 200 C.) was prepared by reducingwith hydrogen an alcoholic solution of the nitro-derivative at roomtemperature using a palladium on carbon catalyst (10% Pd). Thenitro-derivative, i.e. 2-[p'-nitrophenyl] ureidophenol, was obtained bydissolving 10.9 g. of o-aminophenol in dioxane and adding 16.4 g. ofp-nitrophenylisocyanate to the dioxane solution at 15-16 C. Afterpurification from ethanolwater 25 g. of the nitro-derivative (M.P. 213215 C.) was separated.

Coupler III 2.43 g.' of 2-[p'-amin0phenyl] ureidophenol was diluted inpyridine and 1.9 g. of p-toluene sulphonyl chloride was added to thesolution, which then was refluxed for one hour and was mixed withdiluted hydrochloric acid. 3.6 g. of product was obtained which waspurified from ethanol-water. Its melting point was at 183-186 C.

Coupler IV The procedure was the same as in Coupler I, but using2-amino-4-chlorophenol instead of 0amin0phen01. A product with M.P. 205-207 C. was obtained.

Coupler V The procedure was the same as in Coupler I, but replacingo-arnino-phenol with 2-amino-5-methylphenol. After purification, aproduct with M.P. at 192193 C. was obtained.

Coupler VI It was prepared in the same manner as Coupler I, using2-amino-5-methyl-4,6-dichlorophenol instead of oaminophenol. The productobtained had M.P. 232- 234 C.

Coupler VII 10.9 g. of o-aminophenol was added to dioxane, and 21.75 g.of p-isocyano benzene sulphonyl chloride was added to the boilingsolution, which then was refluxed for one hour. This solution was pouredinto another boiling solution of 24.83 g. of p-dodecylaniline in dioxaneand pyridine. 50 g. of product separated. After washing with benzene ithad M.P. 141-144 C.

Coupler VIII The procedure is the same as for Coupler VII, but in thiscase p-dodecylaniline was substituted with 3-amino-5-stearoylaminobenzoic acid. 63 g. of product separated by crystallizingfrom acetonitrile. The melting point was 154-158 C.

Coupler IX 2.43 g. of 2-[p'-aminophenyl] ureidophenol was dispersed indioxane. 2.39 g. of m-chlorosulphobenzoylchloride was added and themixture was refluxed for one hour. The solution was then poured into aboiling solution of 3.76 g. of 3-amino-5-stearoylaminobenzoic acid indioxane and pyridine. After purification with acetone and lightpetroleum (40-70 C.), a product having M.P. 158-162 C., was separated.

Patented May 27, 1969 i 3 Coupler X 2.43 g. of 2-[p-aminophenyl]ureidophenol were dispersed in dioxane and pyridine. 6.21 g. of3-chlorosu1pho (3'-carboxy-5'-stearoylamino) benzanilide was added tothe dispersion at room temperature. A solution was obtained afterrefluxing the dispersion for one hour. The solution was then poured intodilute hydrochloric acid. 7.6 g. of product were purified with acetoneand light petroleum (40-70 C.). M.P. 160-164 C.

3-chlorosulpho-(3-carboxy-5-stearoylamino) benzanilide was prepared byheating to boiling a solution of 3- amino-5-stearoylamino-benzoic acidin acetone. To the solution was added a m-chlorosulphophenzoyl chloride,and the mixture was refluxed for one hour. After it was washed withacetone a product having M.P. 198200 C. was obtained.

Coupler XI The procedure was the same as in Coupler VIII, substituting2-amino-4chlorophenol for o-aminophenol. A product was obtained havingM.P. 168 -l69 C.

Coupler XII The procedure was similar to the preparation of CouplerVIII, substituting 2-amino-4-chlorophenol for o-aminophenol. Afterpurification from ethanol and acetonitrile a product was obtained withM.P. at 174-175 C.

Coupler XIII 12.3 g. of 2-amino-5-methylphenol was diluted in dioxane.21.7 g. of p-isocyano benzene sulfonyl chloride were added to the hotsolution, which was then refluxed for one hour. Then the solution waspoured into a boiling solution of 20.2 g. of tetradecylamine in dioxaneand pyridine. 50 g. of product, having, after crystallization fromacetonltrile, M.P. 148-l52 C., was separated.

Coupler XIV The procedure was the same as in Coupler VII, substitutingZ-amino-S-methylphenol for o-aminophenol. After purification with benzoland light petroleum (70 C.) a product was obtained with M.P. 122- 124 C.

Coupler XV The procedure was the same as Coupler VIII, substituting2-amino5-methylphenol for o-aminophenol. A product was obtained withM.P. 162-164 C.

Coupler XVI The procedure was the same as Coupler XIII, substituting2-amino-S-methyl-4,6-dichlorophenol for o-aminophenol. M.P. 147 -167 C.

Coupler XVII The procedure was the same as Coupler VII, using 2-amino-S-methyl-4,6-dichlorophenol instead of aminophenol. Aftercrystallization from acetonitrile, a product with M.P. 193 l95 C. wasobtained.

Coupler XVIII 4 EXAMPLE 1 A sample photographic element containing alayer of gelatino-silver halide emulsion was exposed and then processedin a color developing bath of the following composition:

The developed material was washed, then processed in a bleaching bath,washed, fixed, washed again and dried. A cyan color image, due to theformation of a dye with maximum absorption at 668 m was obtained.

Similarly, if in the composition of a developing bath, Coupler I issubstituted by Couplers II, III, IV, V, and VI, cyan images are obtainedcontaining dyes with maximum absorptions at 657, 662, 680, 655 and 695mg, respectively.

In the same way, dyes with maximum absorption at 650, 630, 640 and 672 mrespectively are obtained from Compounds 1, 2, 3 and 4 referred to inthe first column of the table.

EXAMPLE 2 A solution made of 10 g. of Coupler VIII, 20 cc. of methanol,and 15 cc. of 2 N NaOH solution and 250 cc. of water was prepared. Thissolution was added, according to the normal technique, to 1 kg. ofsilver halide photographic emulsion, which was then coated onto a base.The photosensitive material so obtained was exposed and then developedin a N,N-diethyl-p-phenylene-diamine color developing bath.

After bleaching and fixing, an image of blue green dye with maximumabsorption at 655 mu, formed in the exposed areas.

Similarly, Couplers VII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, andXVIII can be used to produce dyes with maximum absorptions at 667, 655,652, 668, 658, 648, 655, 640, 656, 668, 652 mg, respectively.

Compounds 5, 6, 7 and 8 of the first column of the table form dyes withmaximum absorption at 627, 630, 618 and 608 mm, respectively.

EXAMPLE 3 Couplers VII, XI, XIII and XVI were also used in the followingmanner.

10 g. of the coupler was added at 50 C. to 20 cc. of dibutyl-phthalateand 60 cc. of ethyl acetate.

This solution was added to 200 cc. of a 4% solution of inert gelatinecontaining also 10 cc. of Tergitol 4 (tetradecyl-sodium sulphonate).This mixture was poured into a homogenizer and the resulting homogenizeddispersion was added to 1 kg. of silver halide photographic emulsion,which was then coated onto a base. The photosensitive material soobtained was exposed and then developed in aN,N-diethyl-p-phenylene-diamine color developing bath. After bleachingand fixing a blue-green image formed in the exposed parts. This image isdue to the formation of dye having maximum absorption as indicated inExample 2.

The above data illustrates the outstanding results achieved withZ-ureido phenols having a p-substituted phenyl group of the formula C HYR, where Y and R are defined above. Preferably R is phenyl (includingsubstituted phenyl), aliphatic (e.g. alkyl), phenylaliphatic (e.g.alkaneamidophenyl) or phenylarylaliphatic (e.g. alkaneamidoanilidophenyl) Various other embodiments of the present inventionwill be apparent to those skilled in the art without departing from thescope thereof.

lrmmo 0426 mO mz o o mz 6 Oiwz o o mz 6 we. we N8 mo J |HO ILWD m8 7 mo8w mo m 6 u 23 mo 3 2* mo N moO om mz O mz o Q mZ O N8 mo E OJETO o mz Oe o mz o mz o o mz 80 mo :4 g m o 3 wan m0 {A 8 .5 52: M 3 588m 200. 62$33; 02 38am 58.5 8 225 .6 6 9834 32 32324 52 in which Y is -NHCO-,-CONH, -NHSO or --SO-,-NH- and R is hydrogen, aryl, alkyl or arylalkyl.

2. The process of claim 1 in which R is phenyl, alkyl, alkylphenyl orarylalkylphenyl.

3. The process of claim 1 in which said amine developer is a p-phenylenediamine compound.

4. A photographic element capable of use in the process of claim 1 andhaving a gelatino silver halide emulsion layer containing as colorcoupler a phenolic compound 2 having in the 2-position a radical of theformula 1 2 NHCONKC YR in which Y is -NHCO, --CONH--, -NHSO, or --SO NH-and R is hydrogen, aryl, alkyl or arylalkyl.

References Cited UNITED STATES PATENTS 2/1945 Porter et al 96-100FOREIGN PATENTS 1,163,144 2/ 1964 Germany.

OTHER REFERENCES Vittum et al., Journal American Chemical Society, vol.68, pp. 2235-9 (1946). I. TRAVIS BROWN, Primary Examiner.

us. 01. X.R.

